Influence of Terminal Carboxyl Groups on the Structure and Reactivity of Functionalized m-Carboranethiolate Self-Assembled Monolayers

Goronzy, Dominic P.; Staněk, Jan; Avery, Erin; Guo, Han; Bastl, Zdeněk; Dušek, Michal; Gallup, Nathan M.; Gün, Saliha; Kučeráková, Monika; Levandowski, Brian J.; Macháček, Jan; Šícha, Václav; Thomas, John C.; Yavuz, Adem; Houk, K. N.; Danışman, Mehmet Fatih; Mete, Ersen; Alexandrova, Anastassia N.; Baše, Tomáš; Weiss, Paul S.

doi:10.1021/acs.chemmater.0c02722

Title: Influence of Terminal Carboxyl Groups on the Structure and Reactivity of Functionalized m-Carboranethiolate Self-Assembled Monolayers

Journal Article · Fri Jul 10 00:00:00 EDT 2020 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.0c02722· OSTI ID:1801660

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^[3]; Bastl, Zdeněk ^[4];

^[5]; Gallup, Nathan M. ^[3]; Gün, Saliha ^[6]; Kučeráková, Monika ^[5];

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^[2]; Šícha, Václav ^[7]; Thomas, John C. ^[1];

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^[10]; Alexandrova, Anastassia N. ^[3]; Baše, Tomáš ^[11];

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Univ. of California, Los Angeles, CA (United States). Dept. of Chemistry and Biochemistry. California NanoSystems Inst.
The Czech Academy of Sciences, Rez (Czech Republic). Inst. of Inorganic Chemistry
Univ. of California, Los Angeles, CA (United States). Dept. of Chemistry and Biochemistry
The Czech Academy of Sciences, Prague (Czech Republic). J. Heyrovský Inst. of Physical Chemistry
The Czech Academy of Sciences, Prague (Czech Republic). Inst. of Physics
Middle East Technical Univ., Ankara (Turkey). Dept. of Chemistry
The Czech Academy of Sciences, Rez (Czech Republic). Inst. of Inorganic Chemistry; Jan Evangelista Purkyne Univ. in Usti nad Labem (Czech Republic). Dept. of Chemistry. Faculty of Science
Middle East Technical Univ., Ankara (Turkey). Micro and Nanotechnology Dept.
Middle East Technical Univ., Ankara (Turkey). Dept. of Chemistry. Micro and Nanotechnology Dept.
Balikesir Univ. (Turkey). Dept. of Physics
Univ. of California, Los Angeles, CA (United States). Dept. of Chemistry and Biochemistry. California NanoSystems Inst.; The Czech Academy of Sciences, Rez (Czech Republic). Inst. of Inorganic Chemistry
Univ. of California, Los Angeles, CA (United States). Dept. of Chemistry and Biochemistry. California NanoSystems Inst. Dept. of Bioengineering. Dept. of Materials Science and Engineering

The structure and function of self-assembled monolayers (SAMs) at the nanoscale are determined by the steric and electronic effects of their building blocks. Carboranethiol molecules form pristine monolayers that provide tunable two-dimensional systems to probe lateral and interfacial interactions. Additional ω-functionality, such as carboxyl groups, can be introduced to change the properties of the exposed surfaces. Here, two geometrically similar isomeric m-carborane analogues of m-mercaptobenzoic acid, 1-COOH-7-SH-1,7-C₂B₁₀H₁₀ and racem-1-COOH-9-SH-1,7-C₂B₁₀H₁₀, are characterized and their SAMs on Au{111} are examined. The latter isomer belongs to the rare group of chiral cage molecules and becomes, to our knowledge, the first example assembled on Au{111}. Although different in symmetry, molecules of both isomers assemble into similar hexagonal surface patterns. The nearest-neighbor spacing of 8.4 ± 0.4 Å is larger than that of non-carboxylated isomers, consistent with the increased steric demands of the carboxyl groups. Computational modeling reproduced this spacing and suggests a tilt relative to the surface normal. However, tilt domains are not observed experimentally, suggesting the presence of strong lateral interactions. Analyses of the influence of the functional groups through the pseudo-aromatic m-carborane skeleton showed that the thiol group attached to either carbon or boron atoms increases the carboxyl group acidity in solution. In contrast, the acidity of the exposed carboxyl group in the SAMs decreases upon surface attachment; computational analyses suggest that the driving force of this shift is the dielectric of the environment in the monolayer as a result of confined intermolecular interactions, proximity to the Au surface, and partial desolvation.

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Research Organization:: Univ. of California, Los Angeles, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0005161; SC0019245

OSTI ID:: 1801660

Journal Information:: Chemistry of Materials, Vol. 32, Issue 15; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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